JP5708134B2 - Decorative sheet and decorative board using the same - Google Patents

Description

  The present invention relates to a decorative sheet and a decorative board using the decorative sheet. Specifically, the present invention relates to a decorative sheet excellent in weather resistance and scratch resistance and a decorative board using the decorative sheet.

In order to give scratch resistance to the decorative sheet, a method of hardening the surface protective layer of the decorative sheet has been taken, but when the decorative sheet is bent or subjected to an impact, cracking or whitening is likely to occur. . On the other hand, if the surface protective layer is soft, scratches are likely to occur, and the surface protective layer may easily dissolve in the solvent.
Therefore, active energy ray-curable urethane (meth) acrylate capable of self-healing even if a fine scratch is once formed on the surface while having elasticity has been proposed (see Patent Document 1). By using it as a protective layer, it is possible to obtain a decorative sheet capable of maintaining excellent impact resistance and scratch resistance without impairing the appearance even after long-term use.

When manufacturing a decorative sheet for exterior use using the above-mentioned self-healing active energy ray-curable urethane (meth) acrylate as a material for forming a surface protective layer, it is necessary to impart weather resistance to the decorative sheet. is there. In order to impart weather resistance, it is common to add weathering agents such as UV absorbers and light stabilizers, but if the type of weathering agent is inappropriate or the amount is low The sufficient weather resistance cannot be imparted.
On the other hand, when the compounding amount of the weathering agent is large, there is a problem of bleeding out.

Japanese Patent Application Laid-Open No. 2002-256053

  The present invention has been made under such circumstances, and an object of the present invention is to provide a decorative sheet having self-repairing properties and excellent weather resistance and scratch resistance, and a decorative board using the decorative sheet. It is.

  As a result of intensive studies to achieve the above object, the inventors of the present invention are decorative sheets having at least a decorative layer, a primer layer, and a surface protective layer in this order on a substrate, and the surface protective layer is a specific sheet. It has been found that a decorative sheet, which is a layer formed by crosslinking and curing an ionizing radiation curable resin composition containing a weathering agent, can meet the purpose. The present invention has been completed based on such findings.

That is, the present invention
(1) A decorative sheet having a decorative layer, a primer layer, and a surface protective layer in this order on a substrate, wherein the surface protective layer is (A) an ionizing radiation curable resin, and (B) a reactive functional group. It is a layer formed by crosslinking and curing an ionizing radiation curable resin composition containing a hindered amine light stabilizer having A and (C) an ultraviolet absorber, and the (A) ionizing radiation curable resin has 13 to 13 carbon atoms. 25 urethane group (meth) acrylate having at least a (meth) acryloyl group as an ionizing radiation curable functional group and a polycaprolactone-modified urethane (meth) acrylate, and the primer layer includes at least an acrylic urethane resin and (C ′ ) a primer layer-forming resin composition containing the ultraviolet absorber, the (C ') an ultraviolet absorber and wherein the non-reactive ultraviolet absorber der Rukoto decorative sheet DOO, and (2) decorative sheet according to (1), an adhesive layer and a decorative laminate having a substrate,
Is to provide.

  ADVANTAGE OF THE INVENTION According to this invention, it can provide the decorative sheet which was especially excellent in the exterior material which has a self-restoration property, and was excellent in a weather resistance, an abrasion resistance, and workability, and a decorative board using the same.

It is a schematic diagram which shows the cross section of the one aspect | mode of the decorative sheet of this invention. It is a schematic diagram which shows the cross section of the other one aspect | mode of the decorative sheet of this invention. It is a schematic diagram which shows the cross section of the one aspect | mode of the decorative board of this invention.

(Layer structure of decorative sheet)
The decorative sheet of the present invention has at least a decorative layer, a primer layer, and a surface protective layer in this order on the substrate. Although there are various modes as the layer structure, typical ones will be described in detail below with reference to FIGS.
The decorative sheet 10 of the present invention shown in FIG. 1 has a decorative layer 12, a primer layer 13, and a surface protective layer 14 in this order on a substrate 11. Moreover, you may provide a back surface primer layer (not shown) on the surface (henceforth a "back surface") opposite to the said each layer of the base material 11 being provided as needed.
Next, in the embodiment shown in FIG. 2, the transparent resin layer 17, the primer layer 13, and the surface protective layer 14 are provided on the base material 11 in this order via the decorative layer 12 and the adhesive layer 16, and are shown in FIG. Similar to the embodiment, the substrate 11 may be provided with a back primer layer (not shown).

(Ionizing radiation curable resin composition)
The decorative sheet of the present invention has an ionizing radiation curing method in which the surface protective layer contains (A) an ionizing radiation curable resin, (B) a hindered amine light stabilizer having a reactive functional group A, and (C) an ultraviolet absorber. A layer obtained by crosslinking and curing the curable resin composition, and the ionizing radiation curable resin (A) has an alkyl group having 13 to 25 carbon atoms and an ionizing radiation curable functional group, and is modified with polycaprolactone. It is a feature.

(Ionizing radiation curable resin)
The component (A) in the present invention is an ionizing radiation curable resin having an alkyl group having 13 to 25 carbon atoms and an ionizing radiation curable functional group and modified with polycaprolactone.
Here, the ionizing radiation curable functional group is a group that crosslinks and cures upon irradiation with ionizing radiation, and preferably includes a functional group having an ethylenic double bond such as a (meth) acryloyl group, a vinyl group, and an allyl group. And at least one selected from these. In the present invention, a (meth) acryloyl group is preferable.
The ionizing radiation means an electromagnetic wave or a charged particle beam having an energy quantum capable of polymerizing or cross-linking molecules, and usually ultraviolet (UV) or electron beam (EB) is used. Electromagnetic waves such as X-rays and γ-rays, and charged particle beams such as α-rays and ion beams can be used. The ionizing radiation curable resin (compound) refers to a resin (compound) that crosslinks and cures when irradiated with the ionizing radiation.

  The (A) ionizing radiation curable resin includes (a) an organic isocyanate having 3 or more isocyanate groups in one molecule, (b) an alcohol having an alkyl group having 13 to 25 carbon atoms, and (c) polycaprolaton. It is obtained by reacting modified hydroxyethyl (meth) acrylate.

The component (a) can be obtained by modifying a diisocyanate monomer by a method such as isocyanurate modification, adduct modification, biuret modification or the like. There is no restriction | limiting in particular as a diisocyanate monomer used here, Tolylene diisocyanate (TDI), Naphthalene diisocyanate (NDI), Diphenylmethane diisocyanate (MDI), Isophorone diisocyanate (IPDI), Xylylene diisocyanate (XDI), Hexamethylene diisocyanate ( HDI).
Next, examples of the component (b) include tridecanol, myristyl alcohol, cetyl alcohol, stearyl alcohol, and behenyl alcohol.
The component (c) is a compound represented by the following general formula (I).

In the formula, R represents a hydrogen atom or a methyl group, and n is an integer of 1 to 25, preferably an integer of 2 to 5. When n is an integer of 2 to 5, curing failure due to an increase in molecular weight between crosslinks is suppressed, and good scratch resistance and self-repair function are exhibited.

In addition, you may use together ionizing radiation-curable resin other than the said (A) component with the ionizing radiation-curable resin composition in this invention.
Further, in the ionizing radiation curable resin composition of the present invention, when an ultraviolet curable resin is used as the ionizing radiation curable resin, the photopolymerization initiator is added in an amount of 0.1 to 100 parts by mass of the ultraviolet curable resin. It is desirable to add about 1 to 5 parts by mass. The initiator for photopolymerization can be appropriately selected from those conventionally used, and is not particularly limited. For example, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin Isobutyl ether, acetophenone, dimethylaminoacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- Hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one, 4- (2-hydroxyethoxy) phenyl-2 (hydroxy-2-propyl) ketone, Nzophenone, p-phenylbenzophenone, 4,4′-diethylaminobenzophenone, dichlorobenzophenone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tertiarybutylanthraquinone, 2-aminoanthraquinone, 2-methylthioxanthone, 2-ethylthioxanthone, Examples include 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, benzyl dimethyl ketal, acetophenone dimethyl ketal and the like.
Moreover, as a photosensitizer, p-dimethylbenzoic acid ester, tertiary amines, a thiol type sensitizer, etc. can be used, for example.

  The ionizing radiation curable resin used in the present invention is preferably electron beam curable. In the case of electron beam curable, solvent-free is possible, which is more preferable from the viewpoint of environment and health, and does not require a photopolymerization initiator, and stable curing characteristics can be obtained.

(Hindered amine light stabilizer having reactive functional group A)
The component (B) in the present invention is a hindered amine light stabilizer having a reactive functional group A (hereinafter sometimes referred to as “reactive HALS”).
The reactive group A in the reactive HALS is not particularly limited as long as it has reactivity with the ionizing radiation curable resin described above. For example, an ethylenic divalent group such as (meth) acryloyl group, vinyl group, allyl group, etc. Preferred examples include a functional group having a heavy bond, and at least one selected from these is preferred. Of these, a (meth) acryloyl group is preferable.

Examples of such reactive HALS include 4- (meth) acryloyloxy-2,2,6,6-tetramethylpiperidine, 4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine, 4- (meth) acryloyloxy-1,2,2,6,6-pentamethylpiperidine, 4- (meth) acryloylamino-1,2,2,6,6-pentamethylpiperidine, 4-cyano-4- (Meth) acryloylamino-2,2,6,6-tetramethylpiperidine, 4-crotonoyloxy-2,2,6,6-tetramethylpiperidine, 4-crotonoylamino-2,2,6,6- Tetramethylpiperidine, 1- (meth) acryloyl-4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine, 1- (meth) acrylo Examples include ru-4-cyano-4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine, 1-crotonoyl-4-crotoyloxy-2,2,6,6-tetramethylpiperidine and the like. It is done.
These reactive HALS may be used individually by 1 type, and may be used in combination of 2 or more type.
The reactive HALS is itself polymerized by irradiation with ionizing radiation to increase its molecular weight or copolymerize with the above-mentioned ionizing radiation curable resin, thereby suppressing bleeding out.

  It is preferable that content of the said reactive HALS is 1-5 mass% with respect to solid content whole quantity in an ionizing radiation-curable resin composition. If the content of the reactive HALS is within the above range, the HALS does not bleed out, and the sheet produced using the coating agent composition of the present invention provides sufficient light stability. Excellent weather resistance is obtained. From the above viewpoint, the content of reactive HALS is more preferably 3 to 5% by mass.

(UV absorber)
The component (C) in the present invention is an ultraviolet absorber (hereinafter sometimes referred to as “UVA”). UVA may be either inorganic or organic. As the inorganic ultraviolet absorber, titanium dioxide, cerium oxide, zinc oxide or the like having an average particle diameter of about 5 to 120 nm can be preferably used. Moreover, as an organic type ultraviolet absorber, a benzotriazole type, a triazine type, a benzophenone type etc. can be used, for example. Examples of the benzotriazole series include 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (2-hydroxy-3,5-di-tert-amylphenyl) benzotriazole, and 3- [ 3- (benzotriazol-2-yl) -5-tert-butyl-4-hydroxyphenyl] propionic acid ester and the like.

  Examples of the triazine series include 2- (2-hydroxy-4- [1-octyloxycarbonylethoxy] phenyl) -4,6-bis (4-phenylphenyl) -1,3,5-triazine, 2- [4 -[(2-hydroxy-3-dodecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2,4-bis [ 2-hydroxy-4-butoxyphenyl] -6- (2,4-dibutoxyphenyl) -1,3,5-triazine, 2- [4-[(2-hydroxy-3-tridecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [4-[(2-hydroxy-3- (2′-ethyl) hexyl)] Oki Ci] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine and the like are preferable, and examples of the benzophenone series include 2,4-dihydroxybenzophenone, 2 2, 2 ', 4-trihydroxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-methoxybenzophenone, and the like.

In the present invention, the use of an ultraviolet absorber having a reactive group B (hereinafter sometimes referred to as “reactive UVA”) as UVA can increase the content without bleeding out. It is preferable in that it can be performed.
As the reactive group B, like the reactive group A, a functional group having an ethylenic double bond such as a (meth) acryloyl group, a vinyl group or an allyl group is preferably exemplified. At least one selected from these groups It is preferable that Of these, a (meth) acryloyl group is preferable.
The reactive HALS and the reactive UVA have a polymerizable group such as a (meth) acryloyl group in the molecule, so that they themselves polymerize and become high molecular weight or coexist with ionizing radiation. (A) Bleed out is suppressed by copolymerizing with ionizing radiation curable resin.

(Other weathering agents)
In the ionizing radiation curable resin composition of the present invention, in addition to the above-described reactive HALS and UVA, other weathering agents, for example, a light stabilizer having no reactive group, as long as the effects of the present invention are not impaired. Can also be used together.
Examples of the light stabilizer having no reactive group include hindered amines, specifically, 2- (3,5-di-tert-butyl-4-hydroxybenzyl) -2′-n-butylmalonate bis (1 , 2,2,6,6-pentamethyl-4-piperidyl), bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, tetrakis (2,2,6,6-tetramethyl-4) -Piperidyl) -1,2,3,4-butanetetracarboxylate and the like.

(Other additives)
In the ionizing radiation curable resin composition of the present invention, various additives can be blended in addition to the above-mentioned weathering agent as long as the object of the present invention is not impaired. Examples of the additive include an abrasion resistance improver, a polymerization inhibitor, a crosslinking agent, an infrared absorber, an antistatic agent, an adhesion improver, a leveling agent, a thixotropic agent, a coupling agent, a plasticizer, Examples include foaming agents, fillers, solvents, and coloring agents.

Examples of the wear resistance improver include particles of α-alumina, silica, kaolinite, iron oxide, diamond, silicon carbide and the like as inorganic materials. Examples of the particle shape include a sphere, an ellipsoid, a polyhedron, a scale shape, and the like. Although there is no particular limitation, a spherical shape is preferable. Organic materials include synthetic resin beads such as cross-linked acrylic resin and polycarbonate resin. The particle size is usually about 30 to 200% of the film thickness. Among these, spherical α-alumina is particularly preferable because it has high hardness and a large effect on improving wear resistance, and it is relatively easy to obtain spherical particles.
Examples of the polymerization inhibitor include hydroquinone, p-benzoquinone, hydroquinone monomethyl ether, pyrogallol, and t-butylcatechol. Examples of the crosslinking agent include a polyisocyanate compound, an epoxy compound, a metal chelate compound, an aziridine compound, and an oxazoline compound. Used.
As the filler, for example, barium sulfate, talc, clay, calcium carbonate, aluminum hydroxide and the like are used.
Examples of the colorant include known coloring pigments such as quinacridone red, isoindolinone yellow, phthalocyanine blue, phthalocyanine green, titanium oxide, and carbon black.
As the infrared absorber, for example, a dithiol metal complex, a phthalocyanine compound, a diimmonium compound, or the like is used.

(Base material)
In the decorative sheet 10 of the present invention, the base material 11 is selected in consideration of suitability for post-processing, and typically a resin film made of a thermoplastic resin is used. As the thermoplastic resin, acrylonitrile-butadiene-styrene resin (hereinafter referred to as “ABS resin”), polyolefin resin such as acrylic resin, polypropylene, polyethylene, polycarbonate resin, vinyl chloride resin, etc. are generally used. Of these, polyolefin resins, polycarbonate resins, and ABS resins are preferable, and polyolefin resins are particularly preferable in the decorative sheet.
Moreover, the said base material can be used as a single layer film of these resin, or a multilayer film by the same kind or different resin.

  Although the thickness of the base material is selected according to the application, it is preferably 50 to 150 μm, more preferably 50 to 120 μm from the viewpoints of workability, flexibility, strength, and the like.

In order to improve the adhesiveness with the layer provided on the base material, the base material can be subjected to physical or chemical surface treatment such as an oxidation method or an unevenness method on one or both sides as desired.
Examples of the oxidation method include corona discharge treatment, plasma treatment, chromium oxidation treatment, flame treatment, hot air treatment, ozone / ultraviolet treatment method, and examples of the unevenness method include sand blast method and solvent treatment method. It is done. These surface treatments are appropriately selected according to the type of the base film, but in general, the corona discharge treatment method is preferably used from the viewpoints of effects and operability.
Further, the base material may be subjected to a treatment such as forming a primer layer, or a coating for adjusting the color or a pattern from a design viewpoint may be formed in advance.

(Decoration layer)
The decorative layer 12 shown in FIG. 1 gives decorativeness to a decorative resin molded product or the like, and may be a colored layer (solid print layer) that is uniformly colored, or prints various patterns with ink. It may be a pattern layer formed by printing using a machine.
Patterns that make up the pattern layer include wood grain patterns, marble patterns such as marble patterns (eg travertine marble patterns), stone patterns simulating the surface of rocks, fabric patterns simulating cloth and cloth patterns, tiled patterns, and brickwork There are patterns, etc., and there are also patterns such as parquet and patchwork that combine these. These patterns are formed by multicolor printing with the usual yellow, red, blue and black process colors, as well as by multicolor printing with special colors prepared by preparing the individual color plates constituting the pattern. Is done.

As the ink used for the decorative layer 12, an ink obtained by appropriately mixing a binder, a colorant such as a pigment or a dye, an extender pigment, a solvent, a stabilizer, a plasticizer, a catalyst, or a curing agent is used. The binder is not particularly limited, and examples thereof include polyurethane resins, vinyl chloride / vinyl acetate copolymer resins, vinyl chloride / vinyl acetate / acrylic copolymer resins, chlorinated polypropylene resins, acrylic resins, and polyesters. Resin, polyamide resin, butyral resin, polystyrene resin, nitrocellulose resin, cellulose acetate resin, etc., any one can be used alone or in combination of two or more. Of these, polyurethane resins are particularly preferred.
Colorants include carbon black (black), iron black, titanium white, antimony white, yellow lead, titanium yellow, petal, cadmium red, ultramarine, cobalt blue and other inorganic pigments, quinacridone red, isoindolinone yellow, phthalocyanine Organic pigments or dyes such as blue, metal pigments made of scaly foil pieces such as aluminum and brass, pearlescent pigments made of scaly foil pieces such as titanium dioxide-coated mica and basic lead carbonate, and the like are used.

The decorative sheet 10 of the present invention may be provided with a concealing layer (not shown) between the base material 11 and the decorative layer 12 as desired. It is provided for the purpose of preventing the pattern color of the decorative sheet 10 from being affected by changes and variations in the color of the surface of the substrate 11. Usually, it is often formed with an opaque color, and a so-called solid printing layer having a thickness of about 1 to 20 μm is preferably used.
Further, a polyolefin-based thermal adhesive layer having a melting point of about 70 to 130 ° C. may be provided between the base material 11 and the decorative layer 12.

(Primer layer)
In the decorative sheet 10 of the present invention, a primer layer 13 is provided between the decorative layer 12 and the surface protective layer 14. By providing the primer layer, the adhesion between the decorative layer 12 and the surface protective layer can be increased, and the stress on the surface protective layer can be relaxed, and cracking due to weathering deterioration of the surface protective layer can be suppressed. Durability can be remarkably improved.

The primer layer 13 is preferably obtained by curing a composition composed of a main component polyol and a curing agent.
Examples of the polyol include polyhydric alcohol, polyether polyol, polyester polyol, polycarbonate polyol, polyolefin polyol, and polyacryl polyol. On the other hand, the curing agent is preferably a polyisocyanate, specifically, an aromatic isocyanate such as 2,4-tolylene diisocyanate, xylylene diisocyanate, naphthalene diisocyanate, 4,4′-diphenylmethane diisocyanate; Aliphatic (or cycloaliphatic) isocyanates such as hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated diphenylmethane diisocyanate; Various adducts or multimers of isocyanates such as tolylene diisocyanate adducts, tolylene diisocyanate trimers, and the like can also be used.
Although the said polyol and polyvalent isocyanate can be used in arbitrary combinations, the acryl urethane type resin formed by making polyacryl polyol and a polyvalent isocyanate compound react and thermosetting is especially preferable.

In the present invention, the primer layer 13 preferably contains (C ′) an ultraviolet absorber (UVA). In particular, the primer layer 13 is preferably formed using a primer layer forming resin composition containing at least the above-mentioned acrylic urethane-based resin and (C ′) ultraviolet absorber. By providing such a primer layer, better weather resistance can be imparted to the decorative sheet of the present invention.
Here, the (C ′) ultraviolet absorber may be the same as the component (C).
The primer layer 13 preferably contains HALS. Here, HALS may be reactive HALS or non-reactive HALS. Here, as HALS, those similar to the above component (B) can be suitably used.

(Surface protective layer)
The surface protective layer 14 in the decorative sheet 10 of the present invention can be formed by applying the above-mentioned ionizing radiation curable resin composition of the present invention on the primer layer 13 and crosslinking and curing it.
Accordingly, the surface protective layer contains a polymer obtained by polymerization of reactive HALS itself, or a copolymer of reactive HALS and ionizing radiation curable resin, thereby suppressing bleeding out of HALS. High weather resistance can be imparted to the surface protective layer.
In addition, the viscosity of this ionizing radiation curable resin composition should just be a viscosity which can form a non-hardened resin layer on the surface of the primer layer 13 by the below-mentioned coating system, and there is no restriction | limiting in particular.
In the present invention, the ionizing radiation curable resin composition is applied to the surface of the primer layer 13 so that the thickness after curing is about 1 to 100 μm, gravure coating, bar coating, roll coating, reverse roll coating, Coating is performed by a known method such as comma coating, preferably gravure coating, to form an uncured resin layer.

In the present invention, the uncured resin layer thus formed is irradiated with ionizing radiation such as an electron beam and ultraviolet rays to cure the uncured resin layer. Here, when an electron beam is used as the ionizing radiation, the acceleration voltage can be appropriately selected according to the resin used and the thickness of the layer, but the uncured resin layer is usually cured at an acceleration voltage of about 70 to 300 kV. preferable.
In addition, in electron beam irradiation, the transmission capability increases as the acceleration voltage increases. Therefore, when a material that deteriorates due to an electron beam is used as the substrate 11, the transmission depth of the electron beam and the thickness of the resin layer are substantially equal. By selecting the acceleration voltage so as to be equal to each other, it is possible to suppress the irradiation of the extra electron beam to the base material 11 and to minimize the deterioration of the base material 11 due to the excess electron beam. .
The irradiation dose is preferably such that the crosslinking density of the resin layer is saturated, usually 5 to 300 kGy (0.5 to 30 Mrad), preferably 10 to 100 kGy (1 to 10 Mrad), more preferably 30 to 70 kGy (3 to 3). 7Mrad).
Further, the electron beam source is not particularly limited. For example, various electron beam accelerators such as a cockroft Walton type, a bandegraft type, a resonant transformer type, an insulated core transformer type, a linear type, a dynamitron type, and a high frequency type. Can be used.

  When ultraviolet rays are used as the ionizing radiation, those containing ultraviolet rays having a wavelength of 190 to 380 nm are emitted. There is no restriction | limiting in particular as an ultraviolet-ray source, For example, a high pressure mercury lamp, a low pressure mercury lamp, a metal halide lamp, a carbon arc lamp, etc. are used.

In this invention, it is preferable that the thickness after hardening of the surface protective layer 14 is 1-100 micrometers. If the thickness of the surface protective layer 14 after curing is 1 μm or more, sufficient physical properties as a protective layer such as scratch resistance and weather resistance can be obtained. On the other hand, when the thickness of the surface protective layer 14 after curing is 100 μm or less, it is easy to uniformly apply ionizing radiation, and it is easy to obtain uniform curing, which is economically advantageous.
In addition, the thickness after curing of the surface protective layer 14 is more preferably 10 to 100 μm from the viewpoint of stably providing self-repairing performance, and further in the range of 10 to 50 μm from the viewpoint of imparting processability. preferable.

(Back primer layer)
In the decorative sheet of this invention, you may provide a back surface primer layer (not shown) in the back surface of a base material. The back primer layer is provided for the purpose of improving the adhesion to the substrate 18 when the decorative board 20 described later is formed. As the material for forming the back primer layer, the same materials as those described for the primer layer 13 can be used.

As shown in FIG. 2, the decorative sheet of the present invention has a mode in which a transparent resin layer 17, a primer layer 13, and a surface protective layer 14 are arranged in this order on a base material 11 via a decorative layer 12 and an adhesive layer 16. It can also be taken.
(Transparent resin layer)
A transparent resin layer 17 may be formed on the decorative layer 12 (or the adhesive layer 16) for the purpose of imparting various performances such as scratch resistance and stain resistance. The transparent resin layer 17 is not particularly limited as long as it is transparent, and includes any of colorless and transparent, colored and transparent, and translucent. Examples of the resin component for forming the transparent resin layer include polyvinyl chloride, polyethylene terephthalate, polybutylene terephthalate, polyamide, polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, and ethylene-acrylic acid. Examples thereof include ester copolymers, ionomers, polymethylpentene, acrylic acid esters, methacrylic acid esters, polycarbonates, and cellulose triacetates. Among the above, polyolefin resins such as polypropylene are preferable. More preferably, it is a polyolefin resin having stereoregularity. When using a polyolefin resin, it is desirable to form a transparent resin layer by extruding a molten polyolefin resin.
For the transparent resin layer, if necessary, a filler, matting agent, foaming agent, flame retardant, lubricant, antistatic agent, antioxidant, ultraviolet absorber, light stabilizer, radical scavenger, soft component ( For example, various additives such as rubber) may be included.
Examples of the method for forming the transparent resin layer include a method of laminating the resin composition containing the resin component and the like on the decorative layer (or adhesive layer) by, for example, a calendar method, an inflation method, a T-die extrusion method, or the like. It is done.
Although the thickness of a transparent resin layer is not specifically limited, Generally, it is preferable to set it as about 20-250 micrometers, especially about 50-200 micrometers.
If necessary, the surface of the transparent resin layer on which the surface protective layer is formed may be subjected to surface treatment such as corona discharge treatment, ozone treatment, plasma treatment, ionizing radiation treatment, or dichromic acid treatment. Good. The surface treatment may be performed according to a conventional method for each treatment.

(Adhesive layer)
The decorative sheet of the present invention preferably has an adhesive layer 16 in order to adhere the decorative layer 12 and the transparent resin layer 17. There is no restriction | limiting in particular as an adhesive agent which comprises the adhesive bond layer 16, Vinyl-type resin, acrylic resin, polyester-type resin, cellulose-type resin etc. are mentioned.

(Manufacturing method of decorative sheet)
In the decorative sheet shown in FIG. 1, for example, a decorative layer 12 is provided on a base material 11 by a known coating method, a primer layer 13 is laminated thereon, and an uncured resin layer is formed on the primer layer. As a coating method, known methods such as gravure coating, bar coating, roll coating, reverse roll coating, comma coating and the like can be used. Thereafter, as described above, the decorative sheet of the present invention can be obtained by irradiating the uncured resin layer with ionizing radiation such as ultraviolet rays and electron beams and curing to form the surface protective layer 14.
In the embodiment shown in FIG. 2, the decoration layer 12 is formed on the base material 11. Next, an adhesive layer 16 is formed on the decorative layer 12 as necessary, and is pasted so that the transparent resin film constituting the transparent resin layer 17 is in contact therewith. Subsequently, the primer layer 13 is laminated | stacked on the transparent resin layer 17, the surface protective layer 14 is formed on this primer layer, and the decorative sheet of this invention shown in FIG. 2 can be obtained. The method for forming the surface protective layer is the same as described above.

(Decorative board)
The decorative sheet 10 of the present invention can be bonded to the substrate 18 through an adhesive layer to obtain a decorative board 20.
The board | substrate 18 used as a to-be-adhered body is not specifically limited, A plastic board, a metal board, woody board | plates, such as a timber, a ceramic material, etc. can be suitably selected according to a use. When these substrates, particularly plastic sheets, are used as substrates, physical or chemical surface treatment such as oxidation or unevenness is optionally applied on one or both sides to improve adhesion to the decorative sheet. Can be applied. As specific examples of the oxidation method and the unevenness method, the same methods as described above can be used.

  It does not specifically limit as an adhesive agent which comprises the adhesive bond layer for bonding the decorative sheet 10 and the board | substrate 18, An epoxy-type adhesive agent, a urethane type adhesive agent, a polyester-type adhesive agent etc. can use it conveniently.

EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.
In addition, the various characteristics of the decorative sheet obtained in each example were evaluated according to the following procedures.

<Evaluation of various properties of decorative sheets>
(1) Bleed property The decorative sheet was left for 2 weeks under conditions of 40 ° C. and 90% relative humidity, and the change of the decorative sheet surface was visually observed. The evaluation criteria are as follows.
○: No change in appearance of the coating film was observed.
Δ: Slight bleeding was observed on the surface of the coating film, but there was no problem in use.
X: Bleed was observed on the surface of the coating film, and there was a problem in use.
(2) Weather resistance Weather resistance evaluation was performed with a weather resistance test apparatus “I Super UV Tester (Iwasaki Electric Co., Ltd., 60 mW / cm ² )”. Evaluation was performed by color change after 100 hours and after 200 hours. The evaluation criteria are as follows.
○: No change in performance / appearance of the coating film was observed.
Δ: A slight change in the performance and appearance of the coating film was observed.
X: The change of the performance and appearance of the coating film was noticeable.

Example 1
(1) Synthesis of electron beam curable resin In a 500 mL flask equipped with a stirrer, a thermometer and a condenser, 57.7 parts by mass of toluene, stearyl alcohol (NAA-46; manufactured by NOF Corporation, hydroxyl value: 207) 9.7 parts by mass were charged and heated to 40 ° C. Thereafter, it was confirmed that stearyl alcohol was completely dissolved, 25 parts by mass of hexamethylene diisocyanate (manufactured by Tokyo Chemical Industry Co., Ltd.) was charged, and the temperature was raised to 70 ° C. After reacting at the same temperature for 30 minutes, 0.02 part by mass of dibutyltin laurate was charged and held at the same temperature for 3 hours. Thereafter, 100 parts by mass of polycaprolactone-modified hydroxyethyl acrylate (Placcel FA2D; manufactured by Daicel Chemical Industries, Ltd., hydroxyl value: 163), 0.02 parts by mass of dibutyltin laurate, 0.02 parts by mass of hydroquinone monomethyl ether were charged. The reaction was terminated by maintaining at 3 ° C. for 3 hours, and 77 parts by mass of toluene was added to obtain urethane acrylate having a solid content of 50% by mass.

(2) Manufacture of decorative sheet After preparing a colored polypropylene resin film (thickness 60 μm) as the base material 11 and applying corona discharge treatment to the surface of the base material, gravure printing a colored solid layer and a woodgrain pattern layer The decorative layer 12 was formed. As the binder resin, a two-component curable urethane resin composed of a urethane acrylic polyol and a hexamethylene diisocyanate curing agent was used for the colored solid layer, and a urethane acrylic polyol resin was used for the pattern layer.
Next, a transparent resin film (thickness 80 μm) obtained by melting a polypropylene thermoplastic elastomer with a T-die is formed, and a coating liquid composed of a two-component curable urethane resin is applied onto the decorative layer 12 to form an adhesive. A layer 16 (thickness 15 μm in a dry state) was formed, and the transparent resin film was laminated by a dry laminating method to form a transparent resin layer 17.
Next, after the corona discharge treatment was performed on the transparent polypropylene layer 17, the following primer layer forming resin composition A (described as A in the table) was applied at a coating amount of 2.5 g / m ² , Primer layer 13 was formed. Next, the following ionizing radiation curable resin composition was applied onto the primer layer by gravure printing at a coating amount of 20 g / m ² to form a coating film. Next, the coating film was crosslinked and cured by irradiation with an electron beam under the conditions of 175 keV and 5 Mrad (50 kGy) to form the surface protective layer 14, and the decorative sheet 10 was obtained. The results of evaluating the decorative sheet by the above method are shown in Table 1. In Example 1, since the layer configuration shown in FIG. 2 was taken, FIG. 2 was described in the column of the layer configuration in the table. In the following examples, those having the configuration of FIG. 2 are described as FIG. 2 in the column of the layer configuration, and those having the configuration of FIG. 1 are described as FIG.

(Primer layer forming resin composition A)
It consists of the following main ingredients, curing agents, extender pigments, and UVA.
Main agent; polyester acrylic urethane resin curing agent having a mass ratio of 5/5 urethane component and acrylic component as binder; hexamethylene diisocyanate (added by 5 parts by mass with respect to 100 parts by mass of main agent)
Extender; untreated silica (commercially available), average particle size of 3 μm, 24% by mass in the primer layer forming resin composition
Non-reactive UVA; triazine-based UV absorber, 11% by mass in the primer layer forming resin composition
(Ionizing radiation curable resin composition)
Ionizing radiation curable resin; electron beam curable resin synthesized in (1) above reactive UVA; 1% by mass in ionizing radiation curable resin composition
Reactive HALS: Trade name “LS-3410” (manufactured by Ciba Japan Co., Ltd.), 1 mass% in ionizing radiation curable resin composition

Examples 2-8
In Example 1, a decorative sheet was obtained in the same manner as in Example 1 except that the primer layer coating amount and the UVA and reactive HALS contents in the surface protective layer were changed as described in Table 1. . The results of evaluation in the same manner as in Example 1 are shown in Table 1.

Examples 9 and 10
In Example 4, a decorative sheet was obtained in the same manner as in Example 1 except that the constitution of the primer layer-forming resin composition was changed as described in Table 1. The results of evaluation in the same manner as in Example 1 are shown in Table 1.
(Primer layer forming resin composition B)
It consists of the following main ingredients, curing agents, extender pigments, and UVA.
Main component: Polycarbonate acrylic urethane resin curing agent having a mass ratio of urethane component to acrylic component as binder of 7/3; hexamethylene diisocyanate (added 5 parts by mass with respect to 100 parts by mass of main agent)
Extender; untreated silica (commercially available), average particle size of 3 μm, 16% by mass in the primer layer forming resin composition
Non-reactive UVA; triazine-based UV absorber, 11% by mass in the primer layer forming resin composition
Non-reactive HALS; trade name “Tinubin 123” (manufactured by Ciba Japan Co., Ltd.), 2% by mass in the resin composition for forming the primer layer

Comparative Examples 1 and 2
In each of Examples 2 and 5, decorative sheets were obtained in the same manner as in Examples 2 and 5 except that reactive HALS was not used. The results of evaluation in the same manner as in Example 1 are shown in Table 1.

Example 11
Example 1 is the same as Example 1 except that the same primer layer forming resin composition A as used in Example 1 was used, and the following ionizing radiation curable resin composition was used for the surface protective layer. A decorative sheet was obtained in the same manner. The results of evaluation in the same manner as in Example 1 are shown in Table 2.
(Ionizing radiation curable resin composition)
Ionizing radiation curable resin; electron beam curable resin non-reactive UVA synthesized in Example 1 (1); triazine ultraviolet absorber, trade name “Tinuvin 479” (manufactured by Ciba Japan Co., Ltd.), ionizing radiation curable 1% by mass in the resin composition
Reactive HALS: Trade name “LS-3410” (manufactured by Ciba Japan Co., Ltd.), 3 mass% in ionizing radiation curable resin composition

Example 12
In Example 11, the layer structure of the decorative sheet is a single layer structure as shown in FIG. 1, that is, the decorative layer 12, the primer layer 13, and the surface protective layer 14 are arranged in this order on the substrate 11. A decorative sheet was obtained in the same manner as Example 11 except for the above. The results of evaluation in the same manner as in Example 1 are shown in Table 2.

Examples 13 and 14
In Examples 11 and 12, decorative sheets were obtained in the same manner as in Examples 11 and 12, except that the ionizing radiation curable resin composition having the composition shown below was used. The results of evaluation in the same manner as in Example 1 are shown in Table 2.
(Ionizing radiation curable resin composition)
Ionizing radiation curable resin; electron beam curable resin reactive UVA synthesized in Example 1 (1); benzotriazole ultraviolet absorber, 3% by mass in ionizing radiation curable resin composition
Reactive HALS: Trade name “LS-3410” (manufactured by Ciba Japan Co., Ltd.), 3 mass% in ionizing radiation curable resin composition
In addition, Example 13 has the layer structure shown in FIG. 2, and Example 14 has the layer structure shown in FIG.

Examples 15 and 16
In Examples 11 and 12, decorative sheets were obtained in the same manner as in Examples 11 and 12, except that the ionizing radiation curable resin composition having the composition shown below was used. The results of evaluation in the same manner as in Example 1 are shown in Table 2.
(Ionizing radiation curable resin composition)
Ionizing radiation curable resin; electron beam curable resin non-reactive UVA synthesized in Example 1 (1); triazine ultraviolet absorber, trade name “Tinuvin 479” (manufactured by Ciba Japan Co., Ltd.), ionizing radiation curable 4% by mass in the resin composition
Reactive UVA; 1% by mass in benzotriazole ultraviolet absorber, ionizing radiation curable resin composition
Reactive HALS: Trade name “LS-3410” (manufactured by Ciba Japan Co., Ltd.), 3 mass% in ionizing radiation curable resin composition
In addition, Example 15 has the layer structure shown in FIG. 2, and Example 16 has the layer structure shown in FIG.

Example 17
In Example 11, the same primer layer forming resin composition B as used in Example 9 was used, and the makeup was made in the same manner as in Example 1 except that the following ionizing radiation curable resin composition was used. A sheet was obtained. The results of evaluation in the same manner as in Example 1 are shown in Table 2.
(Ionizing radiation curable resin composition)
Ionizing radiation curable resin; electron beam curable resin non-reactive UVA synthesized in Example 1 (1); triazine ultraviolet absorber, trade name “Tinuvin 479” (manufactured by Ciba Japan Co., Ltd.), ionizing radiation curable 5% by mass in the resin composition
Reactive UVA; benzotriazole ultraviolet absorber, 3% by mass in ionizing radiation curable resin composition
Reactive HALS: Trade name “LS-3410” (manufactured by Ciba Japan Co., Ltd.), 3 mass% in ionizing radiation curable resin composition

Example 18
In Example 17, the content of the non-reactive triazine UVA in the ionizing radiation curable resin composition was 3% by mass, and the layer structure of the decorative sheet was a single layer structure as shown in FIG. A decorative sheet was obtained in the same manner as in Example 17. The results of evaluation in the same manner as in Example 1 are shown in Table 2.

Example 19
In Example 17, the content of the non-reactive triazine-based UVA in the ionizing radiation curable resin composition was 3% by mass, and the content of the reactive benzotriazole-based UVA was 1% by mass. In the same manner, a decorative sheet was obtained. The results of evaluation in the same manner as in Example 1 are shown in Table 2.

Example 20
In Example 19, a decorative sheet was obtained in the same manner as in Example 19 except that the decorative sheet had a single layer structure as shown in FIG. The results of evaluation in the same manner as in Example 1 are shown in Table 2.

Comparative Examples 3 and 4
In Examples 11 and 12, decorative sheets were obtained in the same manner as in Examples 11 and 12, except that the ionizing radiation curable resin composition having the composition shown below was used. The results of evaluation in the same manner as in Example 1 are shown in Table 2.
(Ionizing radiation curable resin composition)
Ionizing radiation curable resin; electron beam curable resin non-reactive triazine UVA synthesized in Example 1 (1); trade name “Tinuvin 479” (manufactured by Ciba Japan Co., Ltd.), in ionizing radiation curable resin composition 3% by mass
Non-reactive HALS: trade name “Tinubin 123” (manufactured by Ciba Japan Co., Ltd.), 3 mass% in ionizing radiation curable resin composition
Comparative Example 3 has the layer configuration shown in FIG. 2, and Comparative Example 4 has the layer configuration shown in FIG.

Comparative Examples 5 and 6
In Comparative Examples 3 and 4, each was compared except that 3% by mass of reactive UVA (benzotriazole UVA) was used instead of non-reactive UVA (triazine UVA) in the ionizing radiation curable resin composition. A decorative sheet was obtained in the same manner as in Examples 5 and 6. The results of evaluation in the same manner as in Example 1 are shown in Table 2.
Comparative Example 5 has the layer configuration shown in FIG. 2, and Comparative Example 6 has the layer configuration shown in FIG.

The decorative sheet of the present invention has self-healing properties, is excellent in weather resistance and scratch resistance, and has no bleed-out of weathering agents. Therefore, it is possible to maintain the appearance of the cosmetics for a long time, and it is particularly useful as a decorative sheet for exterior use.
[Explanation of symbols]

DESCRIPTION OF SYMBOLS 10 Decorative sheet 11 Base material 12 Decorative layer 13 Primer layer 14 Surface protective layer 16 Adhesive layer 17 Transparent resin layer 18 Substrate 20 Decorative plate

Claims (9)

A decorative sheet having at least a decorative layer, a primer layer and a surface protective layer in this order on a substrate, the surface protective layer having (A) an ionizing radiation curable resin and (B) a reactive functional group A It is a layer formed by crosslinking and curing an ionizing radiation curable resin composition containing a hindered amine light stabilizer and (C) an ultraviolet absorber, and (A) the ionizing radiation curable resin is an alkyl having 13 to 25 carbon atoms. A urethane (meth) acrylate having at least a (meth) acryloyl group as an ionizing radiation-curable functional group and a polycaprolactone-modified urethane, and the primer layer includes at least an acrylic urethane resin and (C ′) ultraviolet absorption decorative sheet made from the primer layer-forming resin composition, and said (C ') an ultraviolet absorber, characterized in der Rukoto nonreactive ultraviolet absorber containing agent.   The decorative sheet according to claim 1, wherein at least a part of the (C) ultraviolet absorber is an ultraviolet absorber having a reactive functional group B.   The decorative sheet according to claim 1 or 2, wherein the content of the component (B) is 1 to 5 mass% with respect to the total solid content in the ionizing radiation curable resin composition.   The decorative sheet according to any one of claims 1 to 3, wherein the content of the component (C) is 1 to 5 mass% with respect to the total solid content in the ionizing radiation curable resin composition.   The decorative sheet according to any one of claims 1 to 4, wherein the number of the ionizing radiation-curable functional groups is 3 or more.   The decorative sheet according to any one of claims 1 to 5, wherein the reactive functional group A is a functional group having an ethylenic double bond.   The decorative sheet according to claim 6, wherein the functional group having an ethylenic double bond is a (meth) acryloyl group. The decorative sheet according to claim 7 , wherein the content of the component (C ') is 1 to 20% by mass with respect to the total solid content in the resin composition for forming a primer layer. A decorative board comprising the decorative sheet according to any one of claims 1 to 8 , an adhesive layer, and a substrate.

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